The present invention relates generally to high solids coating compositions suitable for use, for example, as high performance automotive coatings.
Many of the high performance, high solids automotive coatings presently in use are based upon polymeric systems comprised of either polyester-based or polyacrylic-based polyols and crosslinking agents therefor. These coatings are generally supplied as "one-pack" or "two-pack" systems.
In a typical one-pack system, all of the coating ingredients are combined into one storage stable mixture. Upon application the polyol component is crosslinked, generally with an aminoplast resin (such as a melamine resin) or a blocked isocyanate, under heat cure conditions of 120.degree. C. or above. In a typical two-pack system, the polyol component is combined with a crosslinking agent, generally an isocyanate, shortly before application, with curing being conducted at ambient or elevated temperatures.
For environmental reasons, it is becoming increasingly important to develop polymeric systems with low solution viscosities, which permit the formulation of high solids coatings with low application viscosities suitable for spraying. High solids coatings (generally about 50 wt % or greater solids) significantly decrease the amount of volatile organic compounds (VOC) entering the atmosphere upon drying/curing of the coating.
To achieve acceptable solution viscosities (20-30 seconds, #4 Ford Cup at 20.degree. C.) for typical high solids coating systems, the polyols should possess a weight average molecular weight (Mw) of about 5000 or lower. In general, the lower the Mw the lower the solution viscosity.
To achieve good film properties it is important that, upon film formation, the polyol molecules become sufficiently chemically bonded to each other. This can be accomplished by providing each polyol molecule with at least two reactive hydroxyl groups. A too low hydroxyl equivalent weight (HEW) (e.g., below about 200), however, may lead to brittle films. It has been found that, in general, the best spectrum of film properties may be obtained for HEWs between about 300 to 500. It follows, therefore, that for good film formation the polyols should possess a number average molecular weight (Mn) of at least about 800.
As is evident from the above discussion, the requirements for acceptable solution viscosities and good film properties lead to contradictory molecular weight requirements--for low solution viscosities the Mw should be low, but for good film properties the Mn should be high.
In acrylic free radical polymerization and in polycondensation leading to polyesters, it is difficult to achieve desirable molecular weights with sufficiently narrow molecular weight distributions. In other words, it is difficult to formulate high solids, high performance coating systems from acrylic and/or polyester based polyols which possess both acceptable application viscosities and resulting film properties.
A considerable amount of work in this area has recently been done relating to high solids, high performance coatings which are based, in part, upon relatively low molecular weight polyesterurethane, urethane-modified polyester and polyurethane polyols.
For example, U.S. Pat. Nos. 4,485,228, 4,540,766, 4,540,771 and U.S. Pat. No. 4,605,724 describe high solids coating systems based, in part, upon relatively low molecular weight polyesterurethane polyols and crosslinking agents therefor. More particularly, U.S. Pat. No. 4,485,228 describes a two-pack system with a polyisocyanate crosslinker, while U.S. Pat. No. 4,540,766 describes a one-pack system with an aminoplast or blocked isocyanate crosslinker. The polyesterurethane polyols of these references are produced via the reaction of a polyisocyanate with a stoichiometric excess of a polyester polyol.
In related U.S. Pat. No. 4,543,405 are disclosed high solids coatings based upon low molecular weight polyurethane polyols and/or higher molecular weight prepolymers (e.g., urethane-modified polyesters), which polyurethane polyols are produced by reacting a polyisocyanate with a large excess of a polyol. After completion of the reaction, the excess polyol is removed, e.g., by distillation. Also relevant in this aspect is U.S. Pat. No. 4,288,577.
U.S. Pat. No. 4,548,998, like those references just mentioned, describes a high solids coating system based upon a polyesterurethane polyol, except that the polyesterurethane polyol is produced by isocyanate-free reaction of a polyester polyol, urea and a polyamine.
U.S. Pat. Nos. 4,524,192, 4,530,976, 4,533,703, 4,533,704 and EP-A-0139513 describe similar high solids coating systems which are based, in part, upon urethane-modified polyester polyols and crosslinking agents therefor. The urethane-modified polyester polyols are produced by reacting a urethane-modified diol component (from a diol and diisocyanate) with a diacid component and a second polyol including at least 5 wt % triol.
Finally, U.S. Pat. Nos. 4,544,188 and 4,559,383 both disclose high solids, organic solvent based coating compositions based upon a particular urethane modified polyhydroxy oligomer and an hydroxyl group reactive crosslinking agent. The urethane modified polyhydroxy oligomer contains at least two hydroxyl groups and a single blocked isocyanate group, and is produced by reacting a polyol comprising three or more hydroxyl groups and a half-blocked diisocyanate.
As mentioned above, due to environmental concerns it is becoming increasingly important to reduce the VOC of coatings in general. Additionally, due to the current deterioration of the environment and, particularly, the proliferation of acid rain, it is also becoming increasingly important that such coatings, upon curing drying, display improved acid etch resistance.
To obtain high solids content while maintaining acceptable viscosity for spray application, the industry has tended to decrease the Mn of the acrylic and polyester based polyols and increase the amount of crosslinker. Many of the state-of-the-art high solids systems, especially the one-pack systems, utilize aminoplast resins (such as hexamethoxymelamine resins) as the crosslinker. Generally, however, as the amount of aminoplast resin is increased, the acid etch resistance of these coatings is compromised. It is believed that the ester bonds in acrylic/melamine or polyester/melamine coatings are weak points in the crosslinked network, and susceptible to acid catalyzed hydrolysis.
Others of the aforementioned systems, formulated as two-pack systems with isocyanate crosslinkers, provide better acid etch resistance; however, the use of isocyanates has a number of disadvantages. For example, these two-pack systems require special handling and storage operations to avoid human exposure to the toxic isocyanates. Further, the components can only be mixed shortly prior to use, often resulting in mixing errors which can adversely affect the quality of the resulting coating.
It would, therefore, also be advantageous to provide a one-pack, high solids system which displays a good balance of physical and chemical properties and, especially, good acid etch resistance.